U.S. patent number 7,988,776 [Application Number 12/056,859] was granted by the patent office on 2011-08-02 for coloring composition, thermal transfer recording ink sheet, thermal transfer recording method, color toner, inkjet ink, color filter, and azo dye.
This patent grant is currently assigned to Fujifilm Corporation. Invention is credited to Yoshihiko Fujie, Hisashi Mikoshiba, Naotsugu Muro.
United States Patent |
7,988,776 |
Fujie , et al. |
August 2, 2011 |
Coloring composition, thermal transfer recording ink sheet, thermal
transfer recording method, color toner, inkjet ink, color filter,
and azo dye
Abstract
A coloring composition containing an azo dye of the following
formula (1): ##STR00001## wherein R.sup.1, R.sup.2, R.sup.3 and
R.sup.6 represent a monovalent substituent; R.sup.5 represents a
hydrogen atom or a monovalent substituent; n is 0 to 4.
Inventors: |
Fujie; Yoshihiko (Kanagawa,
JP), Mikoshiba; Hisashi (Kanagawa, JP),
Muro; Naotsugu (Kanagawa, JP) |
Assignee: |
Fujifilm Corporation (Tokyo,
JP)
|
Family
ID: |
39672003 |
Appl.
No.: |
12/056,859 |
Filed: |
March 27, 2008 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20080248202 A1 |
Oct 9, 2008 |
|
Foreign Application Priority Data
|
|
|
|
|
Mar 30, 2007 [JP] |
|
|
2007-092233 |
|
Current U.S.
Class: |
106/31.5;
534/753 |
Current CPC
Class: |
C09B
67/0083 (20130101); B41M 5/388 (20130101); C09B
29/0037 (20130101); C09B 29/081 (20130101); C09D
11/328 (20130101); C09D 11/037 (20130101); G02B
5/201 (20130101) |
Current International
Class: |
C09D
11/02 (20060101); C09B 29/036 (20060101) |
Field of
Search: |
;106/31.5 ;534/753
;428/195.1 ;430/7,108.23,200 ;347/100 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
43 43 454 |
|
Jun 1995 |
|
DE |
|
0 484 814 |
|
May 1992 |
|
EP |
|
0 492 444 |
|
Jul 1992 |
|
EP |
|
2 065 693 |
|
Jul 1981 |
|
GB |
|
Other References
An Extended European Search Report dated Aug. 19, 2008. cited by
other.
|
Primary Examiner: Klemanski; Helene
Attorney, Agent or Firm: Sughrue Mion, PLLC
Claims
What is claimed is:
1. A coloring composition containing an azo dye of the following
formula (1): ##STR00013## wherein R.sup.1 and R.sup.2 each
independently represents an unsubstituted aliphatic group having
from 1 to 10 carbon atoms, R.sup.3 and R.sup.6 each independently
represents a monovalent substituent; R.sup.5 represents a hydrogen
atom or a monovalent substituent; n indicates an integer of from 0
to 4; when n is 2 or more, plural R.sup.3's may be the same or
different; and R.sup.1 and R.sup.2 may bond to each other to form a
cyclic structure.
2. A thermal transfer recording ink sheet containing the azo dye of
claim 1.
3. A thermal transfer recording method comprising forming an image
by utilizing the thermal transfer recording ink sheet of claim 2 on
an image-receiving material comprising a polymer-containing
ink-receiving layer on a support.
4. A color toner containing the azo dye of claim 1.
5. An inkjet ink containing the azo dye of claim 1.
6. A color filter containing the azo dye of claim 1.
7. An azo dye of the following formula (2): ##STR00014## wherein
R.sup.1 and R.sup.2 each independently represents an unsubstituted
aliphatic group having from 1 to 10 carbon atoms, R.sup.3, R.sup.4
and R.sup.6 each independently represents a monovalent substituent;
R.sup.5 represents a hydrogen atom or a monovalent substitutent; m
indicates an integer of from 0 to 3; when m is two or more, plural
R.sup.3's may be the same or different; and R.sup.1 and R.sup.2 may
bond together to form a cyclic structure.
8. The coloring composition according to claim 1, wherein R.sup.1
and R.sup.2 each independently represents an unsubstituted
aliphatic group having from 1 to 4 carbon atoms.
9. The coloring composition according to claim 1, wherein R.sup.5
represents a tert-butyl group.
10. The azo dye according to claim 7, wherein R.sup.1 and R.sup.2
each independently represents an unsubstituted aliphatic group
having from 1 to 4 carbon atoms.
11. The azo dye according to claim 7, wherein R.sup.5 represents a
tert-butyl group.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a coloring composition containing
a specific azo dye, a thermal transfer recording ink sheet, a
thermal transfer recording method, a color toner, an inkjet ink, a
color filter, and a specific novel azo dye.
2. Background Art
These days, in particular, a color image-forming material is the
mainstream of an image-recording material; and concretely,
inkjet-type recording materials, thermal transfer-type recording
materials, electrophotographic recording materials, transfer-type
silver halide photosensitive materials, printing inks and recording
pens are much used. In an image sensor such as CCD as photography
machinery and in LCD or PDP as displays, a color filter is used for
recording and reproducing color images.
In a color image-recording material and a color filter, used are
colorants (dyes, pigments) of three primary colors for an additive
mixture process or a subtractive mixture process. At present,
however, no one could find a fast colorant that has absorption
characteristics capable of realizing a favorable color reproduction
range and is durable to various conditions in practical use, and it
is strongly desired to improve colorants.
Thermal transfer recording includes a recording system where a
thermal transfer material having a thermofusible ink layer formed
on a support (base film) is heated with a thermal head to thereby
melt the ink for recording on an image-recording material, and a
recording system where a thermal transfer material having a
transferable dye-containing dye-donating layer formed on a support
is heated with a thermal head to thereby thermally diffuse and
transfer the dye onto an image-receiving material. In the latter
thermal transfer system, the dye transfer rate may be varied by
changing the energy to be applied to the thermal head, therefore
facilitating gradation recording, and the system is especially
advantageous for high-quality full-color recording. However, the
transferable dye for use in this system has various limitations,
and only an extremely few dyes are known capable of satisfying all
the necessary performance requirements.
The performance requirements include, for example, spectral
characteristics favorable for color reproduction, easy
transferability, fastness to light and heat, fastness to various
chemicals, easy producibility, and easy workability to construct
thermal transfer recording materials. However, conventional
specific dyes that have been proposed as those having spectral
characteristics favorable for color reproduction and having
fastness to light and heat (for example see Patent JP-A 1-225592
and JP-A 63-189289) could not be on a satisfactory level, and
further improvements are strongly desired.
In color copiers and color laser printers to be driven by
electrophotography, in general, a toner is widely used that
comprises a colorant dispersed in resin particles. The performance
requirements for the color toner include absorption characteristics
capable of realizing a preferred color reproduction range,
especially high transmittance (transparency) required in use in
overheat projectors (hereinafter referred to as CHP), and various
fastness requirements under environmental conditions in practical
use. A toner comprising a pigment colorant dispersed in particles
has been proposed (for example, see JP-A 62-157051, JP-A 62-255956
and JP-A 6-118715). The toner of the type may have excellent light
fastness, but may readily aggregate as being insoluble and is
problematic in point of the transparency reduction and the
transmitted color shift. On the other hand, a toner comprising a
specific dye as a colorant has also been proposed (for example, see
JP-A 3-276161, JP-A 2-207274 and JP-A 2-207273), and the toner of
the type has high transparency and is free from the problem of
color shift contrary to the above, but is problematic in point of
the light fastness.
An inkjet recording method has been rapidly popularized and is
being developed further more, since its material cost is low, it
enables high-speed recording, it is noiseless in recording
operation, and it facilitates color recording.
The inkjet recording method includes a continuous system of
continuously jetting out ink droplets and an on-demand system of
jetting out ink droplets in accordance with image information
signals; and the jetting system includes a system of jetting out
ink droplets under pressure given thereto by a piezo device, a
system of jetting out ink droplets by generating bubbles in ink by
heat, a system of using ultrasonic waves, and a system of
electrostatically sucking and jetting out ink droplets. As the
inkjet recording ink, usable is water-base ink, oily ink, or solid
(fusible) ink.
The requirements for the colorant to be used in the inkjet
recording ink are that it well dissolves or disperses in solvent,
it enables high-density recording, its color is good, it is fast to
light, heat, active gases in the environment (e.g., oxidizing gas
such as NOx, SOx, ozone), it is fast to water and chemicals, it may
well fix in image-receiving material and hardly blurs it, it is
well storable as ink, it is nontoxic, its purity is high, and it is
inexpensive and easily available. However, it is extremely
difficult to obtain a colorant that satisfies all these
requirements at a high level. In particular, it is strongly desired
to obtain a colorant that has a good magenta color tone, has high
solubility, and is fast to light, humidity and heat, especially
highly fast to light.
A color filter is required to have high transparency, for which,
therefore, employed is a dyeing method of coloration with a dye.
For example, a method that comprises patterning exposure and
development of a dyeable photoresist to form a pattern, and then
dyeing it with a filter color dye is successively repeated for all
filter colors to produce a color filter. Apart form the dyeing
method, a method of using a positive resist may also be employed
for producing a color filter. The color filters produced according
to these methods may have high transparency and excellent optical
properties as using dyes, but their light fastness and heat
resistance are limited. Accordingly, a colorant having excellent
fastness and having high transparency is desired. On the other
hand, A method of using an organic pigment having excellent light
fastness and heat resistance in place of dye is widely known, but
pigment-containing color filters could hardly have good optical
properties like those of dye-containing color filters.
Common to those for use in the above-mentioned applications, the
dyes are desired to have the following properties. Specifically,
they have a color favorable for color reproduction, they have an
optimum spectral absorption, their fastness such as light fastness,
moisture fastness, chemical fastness is good, their solubility is
high.
For use in thermal transfer recording, dyes having a specific
pyrazolylazoaniline skeleton have been proposed (for example, see
U.S. Pat. No. 4,764,178 and JP-A 4-265797). However, the dyes could
not always satisfy the above-mentioned requirements for their
properties on a satisfactory level, and further investigations are
desired.
SUMMARY OF THE INVENTION
An object of the invention is to provide a thermal transfer
recording ink sheet and a thermal transfer recording method, in
which an azo dye having excellent spectral characteristics with
sharp absorption and having high fastness is used to satisfy all
the requirements of excellent color reproducibility, image
storability and transfer sensitivity in print samples. Another
object of the invention is to provide the azo dye having excellent
solubility. Still another object of the invention is to provide a
color toner, an inkjet ink and a color filter comprising the azo
dye. Still another object of the invention is to provide a novel
azo dye having a specific substituent, which has especially
excellent spectral characteristics with sharp absorption and has
high fastness.
The present inventors have assiduously studied and, as a result,
have found that the above-mentioned objects can be attained by the
following constitution:
[1] A coloring composition containing an azo dye of the following
formula (1):
##STR00002## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.6 each
independently represent a monovalent substituent; R.sup.5
represents a hydrogen atom or a monovalent substituent; n indicates
an integer of from 0 to 4; when n is 2 or more, plural R.sup.3's
may be the same or different; and R.sup.1 and R.sup.2 may bond to
each other to form a cyclic structure.
[2] A thermal transfer recording ink sheet containing the azo dye
of the above [1].
[3] A thermal transfer recording method comprising forming an image
by use of the thermal transfer recording ink sheet of the above [2]
on an image-receiving material comprising a polymer-containing
ink-receiving layer on a support.
[4] A color toner containing the azo dye of the above [1].
[5] An inkjet ink containing the azo dye of the above [1].
[6] A color filter containing the azo dye of the above [1].
[7] An azo dye of the following formula (2):
##STR00003## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.6
each independently represent a monovalent substituent; R.sup.5
represents a hydrogen atom or a monovalent substituent; m indicates
an integer of from 0 to 3; when m is 2 or more, plural R.sup.3's
may be the same or different; and R.sup.1 and R.sup.2 may bond to
each other to form a cyclic structure.
According to the invention, there are provided a novel azo dye
satisfying all the requirements of excellent spectral
characteristics with sharp absorption, high fastness and excellent
transfer sensitivity; a thermal transfer recording ink sheet
containing the azo dye; and a thermal transfer recording method
using it. Unexpectedly, the novel azo dye has excellent solubility
in solvent, and it greatly reduces the working load and the
environmental load in ink sheet formation with it. Accordingly, the
invention provides a thermal transfer recording ink sheet and a
thermal transfer recording method capable of satisfying all the
requirements of excellent color reproducibility, image storability
and transfer sensitivity in print samples. Further, the invention
provides a color toner, an inkjet ink and a color filter comprising
the azo dye.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a reflection spectrum of the image obtained in the inkjet
recording in the example.
FIG. 2 is a transmission spectrum of the color filter produced in
the example.
BEST MODE FOR CARRYING OUT THE INVENTION
The thermal transfer recording ink sheet, the color toner, the
inkjet ink and the color filter and also the azo dye for use in
these of the invention are described in detail hereinunder.
The description of the constitutive elements of the invention given
hereinunder is for some typical embodiments of the invention, to
which, however, the invention should not be limited. In this
description, the numerical range expressed by the wording "a number
to another number" means the range that falls between the former
number indicating the lowermost limit of the range and the latter
number indicating the uppermost limit thereof.
[Azo Dye of Formula (1)]
First described is the azo dye of formula (1) of the invention.
The azo dye of formula (1) (pyrazolylazoaniline dye) is a dye
characterized by having a sulfonyl group introduced as a
1-positioned substituent of pyrazole. The azo dye having such a
characteristic structure is described in U.S. Pat. No. 3,515,715 as
an example of synthetic intermediates therein; and no one knows at
all the applicability of the azo dye having such a characteristic
structure favorably to a coloring composition, a thermal transfer
recording ink sheet, a thermal transfer recording method, a color
toner, an inkjet ink, a color filter, etc. As compared with a dye
having a hydrogen atom or an alkyl group as the 1-positioned
substituent of pyrazole, the azo dye of formula (1) has
overwhelmingly excellent light fastness. It may be because of the
steric effect near the azo group or because of the oxidative fading
retardation owing to the increase in the oxidation potential of the
dye in which the sulfonyl group has an electron-attracting
capability; but the details are unknown.
The azo dye of formula (1) has excellent solubility and light
fastness and is favorable for thermal transfer recording ink
sheets, and in addition, it may also be favorably used in other
applications (for example, ink).
In formula (1), R.sup.1 and R.sup.2 each independently represent a
monovalent substituent.
The substituent is not specifically defined. Its typical examples
include an aliphatic group (e.g., alkyl group, alkenyl group,
alkynyl group), an aryl group, a heterocyclic group, an acyl group,
an aryloxycarbonyl group, an aliphatic oxycarbonyl group (e.g.,
alkoxycarbonyl group), a carbamoyl group; and these may be further
substituted. The substituents for them are described
separately.
R.sup.1 and R.sup.2 may bond to each other to form a cyclic
structure. The cyclic structure is preferably a 5- to 7-membered
cyclic structure, more preferably a 5- or 6-membered cyclic
structure. Examples of the cyclic structure to be formed by
R.sup.1, R.sup.2 and the nitrogen atom to which they bond include a
pyrrolidine ring, a piperidine ring, a morpholine ring, preferably
a piperidine ring, a morpholine ring.
In formula (1), R.sup.3 represents a substituent, and R.sup.5
represents a hydrogen atom or a substituent. The substituent for
R.sup.3 and R.sup.5 is not specifically defined. Its typical
examples include a halogen atom, an aliphatic group [a saturated
aliphatic group (this means an alkyl group, or a cyclic saturated
aliphatic group including a cycloalkyl group, a bicycloalkyl group,
a crosslinked cyclic saturated hydrocarbon group, a spiro-saturated
hydrocarbon group), an unsaturated aliphatic group (this means a
linear unsaturated aliphatic group having a double bond or a triple
bond, such as an alkenyl group, an alkynyl group; or a cyclic
unsaturated aliphatic group including a cycloalkenyl group, a
bicycloalkenyl group, a crosslinked cyclic unsaturated hydrocarbon
group, a spiro-unsaturated hydrocarbon group)], an aryl group
(preferably a phenyl group optionally having a substituent), a
heterocyclic group (preferably a 5- to 8-membered, alicyclic,
aromatic or heterocyclic ring having an oxygen atom, a sulfur atom
or a nitrogen atom as the ring-constitutive atom, and it may be a
condensed ring), a cyano group, an aliphatic oxy group (typically
an alkoxy group), an aryloxy group, an acyloxy group, a
carbamoyloxy group, an aliphatic oxycarbonyloxy group (typically an
alkoxycarbonyloxy group, an aryloxycarbonyloxy group), an amino
group [including an aliphatic amino group (typically an alkylamino
group), an anilino group, a heterocyclic amino group], an acylamino
group, an aminocarbonylamino group, an aliphatic oxycarbonylamino
group (typically an alkoxycarbonylamino group), an
aryloxycarbonylamino group, a sulfamoylamino group, an aliphatic
(typically an alkyl) or aryl sulfonylamino group, an aliphatic thio
group (typically an alkylthio group), an arylthio group, a
sulfamoyl group, an aliphatic (typically an alkyl) or arylsulfinyl
group, an aliphatic (typically an alkyl) or arylsulfonyl group, an
acyl group, an aryloxycarbonyl group, an aliphatic oxycarbonyl
group (typically an alkoxycarbonyl group), a carbamoyl group, an
aryl or heterocyclic azo group, an aliphatic oxysulfonyl group
(typically an alkoxysulfonyl group), an aryloxysulfonyl group, a
halogen atom, a hydroxyl group, a nitro group, a carboxyl group, a
sulfo group. These groups may be further substituted (for example,
with the substituent mentioned in the above for R.sup.3).
In formula (1), R.sup.6 represents a substituent. The substituent
is not specifically defined. Its typical examples include the
substituents mentioned in the above for R.sup.3, especially an
aliphatic group (typically an alkyl group, an alkenyl group, an
alkynyl group, a cycloalkyl group, a cycloalkenyl group), an aryl
group, a heterocyclic group, an amino group [including an amino
group, an aliphatic amino group (typically an alkylamino group), an
anilino group, a heterocyclic amino group]; and these groups may be
further substituted (for example, with the substituent mentioned in
the above for R.sup.3).
The substituents of R.sup.1, R.sup.2, R.sup.3, R.sup.5 and R.sup.6,
and the substituents which these groups may optionally have are
described in more detail hereinunder.
The halogen atom includes a fluorine atom, a chlorine atom, a
bromine atom and an iodine atom. Above all, preferred are a
Chlorine atom and a bromine atom; and more preferred is a chlorine
atom.
The aliphatic group is a linear, branched or cyclic aliphatic
group; and as so mentioned in the above, the saturated aliphatic
group includes an alkyl group, a cycloalkyl group, a bicycloalkyl
group; and these may be further substituted. Preferably, the number
of the carbon atoms constituting the group is from 1 to 30. Its
examples include a methyl group, an ethyl group, an n-propyl group,
an isopropyl group, a tert-butyl group, an n-octyl group, an
eicosyl group, a 2-chloroethyl group, a 2-cyanoethyl group, a
benzyl group, a 2-ethylhexyl group. The cycloalkyl group includes a
substituted or unsubstituted cycloalkyl group. For the substituted
or unsubstituted cycloalkyl group, the cycloalkyl group preferably
has from 3 to 30 carbon atoms. Its examples include a cyclohexyl
group, a cyclopentyl groups a 4-n-dodecylcyclohexyl group. The
bicycloalkyl group is a substituted or unsubstituted bicycloalkyl
group having from 5 to 30 carbon atoms, or that is, a monovalent
group derived from a bicycloalkane having from 5 to 30 carbon atoms
by removing one hydrogen atom therefrom. Its examples include a
bicyclo[1.2.2]heptan-2-yl group, a bicyclo[2.2.2]octan-3-yl group.
It further includes a tricyclo structure and more multi-cyclo
structures.
The unsaturated aliphatic group is a linear, branched or cyclic
unsaturated aliphatic group, including an alkenyl group, an
cycloalkenyl group, a bicycloalkenyl group, an alkynyl group. The
alkenyl group is a linear, branched or cyclic, substituted or
unsubstituted alkenyl group. Preferably, the alkenyl group is an
unsubstituted or substituted alkenyl group having from 2 to 30
carbon atoms. Its examples include a vinyl group, an allyl group, a
prenyl group, a geranyl group, an oleyl group. The cycloalkenyl
group is preferably a substituted or unsubstituted cycloalkenyl
group having from 3 to 30 carbon atoms, or that is, a monovalent
group derived from a cycloalkene having from 3 to 30 carbon atoms
by removing one hydrogen atom therefrom. Its examples include a
2-cyclopenten-1-yl group, a 2-cyclohexen-1-yl group. The
bicycloalkenyl group includes a substituted or unsubstituted
bicycloalkenyl group. The bicycloalkenyl group is preferably a
substituted or unsubstituted bicycloalkenyl group having from 5 to
30 carbon atoms, or that is, a monovalent group derived from a
bicycloalkene having one double bond by removing one hydrogen atom
therefrom. Its examples include a bicyclo[2.2.1]hept-2-en-1-yl
group, a bicyclo[2.2.2]oct-2-en-4-yl group. The alkynyl group is
preferably a substituted or unsubstituted alkynyl group having from
2 to 30 carbon atoms, including, for example, an ethynyl group, a
propargyl group.
The aryl group is preferably a substituted or unsubstituted aryl
group having from 6 to 30 carbon atoms, including, for example, a
phenyl group, a p-tolyl group, a naphthyl group, a m-chlorophenyl
group, an o-hexadecanoylaminophenyl group. Preferred is a phenyl
group optionally having a substituent.
The heterocyclic group is a monovalent group derived from a
substituted or unsubstituted, aromatic or non-aromatic heterocyclic
compound by removing one hydrogen atom therefrom, and it may form a
condensed ring. The heterocyclic group is preferably a 5- or
6-membered heterocyclic group, and the ring-constituting hetero
atom is preferably an oxygen atom, a sulfur atom, a nitrogen atom.
More preferably, it is a 5- or 6-membered aromatic heterocyclic
group having from 3 to 30 carbon atoms. The hetero ring of the
heterocyclic group includes a pyridine ring, a pyrazine ring, a
pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline
ring, an isoquinoline ring, a quinazoline ring, a cinnoline ring, a
phthalazine ring, A quinoxaline ring, a pyrrole ring, an indole
ring, a furan ring, a benzofuran ring, a thiophene ring, a
benzothiophene ring, a pyrazole ring, an imidazole ring, a
benzimidazole ring, a triazole ring, an oxazole ring, a benzoxazole
ring, a thiazole ring, a benzothiazole ring, an isothiazole ring, a
benzisothiazole ring, a thiadiazole ring, an isoxazole ring, a
benzisoxazole ring, a pyrrolidine ring a piperidine ring, a
piperazine ring, an imidazolidine ring, a thiazoline ring.
The aliphatic oxy group (typically alkoxy group) includes a
substituted or unsubstituted aliphatic oxy group (typically alkoxy
group), and preferably has from 1 to 30 carbon atoms. For example,
it includes a methoxy group, an ethoxy group, an isopropoxy group,
an n-octyloxy group, a methoxyethoxy group, a hydroxyethoxy group,
a 3-carboxypropoxy group.
The aryloxy group is preferably a substituted or unsubstituted
aryloxy group having from 6 to 30 carbon atoms. Examples of the
aryloxy group include a phenoxy group, a 2-methylphenoxy group, a
4-tert-butylphenoxy group, a 3-nitrophenoxy group, a
2-tetradecanoylaminophenoxy group. Preferred is a phenyloxy group
optionally having a substituent.
The acyloxy group is preferably a formyloxy group, a substituted or
unsubstituted alkylcarbonyloxy group having from 2 to 30 carbon
atoms, or a substituted or unsubstituted arylcarbonyloxy group
having from 6 to 30 carbon atoms. Examples of the acyloxy group
include a formyloxy group, an acetyloxy group, a pivaloyloxy group,
a stearoyloxy group, a benzoyloxy group, a
p-methoxyphenylcarbonyloxy group.
The carbamoyloxy group is preferably a substituted or unsubstituted
carbamoyloxy group having from 1 to 30 carbon atoms. Examples of
the carbamoyloxy group include an N,N-dimethylcarbamoyloxy group,
an N,N-diethylcarbamoyloxy group, a morpholinocarbonyloxy group, an
N,N-di-n-octylaminocarbonyloxy group an N-n-octylcarbamoyloxy
group.
The aliphatic oxycarbonyloxy group (typically alkoxycarbonyloxy
group) preferably has from 2 to 30 carbon atoms, and it may have a
substituent. For example, it includes a methoxycarbonyloxy group,
an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, an
n-octylcarbonyloxy group.
The aryloxycarbonyloxy group is preferably a substituted or
unsubstituted aryloxycarbonyloxy group having from 7 to 30 carbon
atoms. Examples of the aryloxycarbonyloxy group include a
phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, a
p-n-hexadecyloxyphenoxycarbonyloxy group. Preferred is a
phenoxycarbonyloxy group optionally having a substituent.
The amino group includes an amino group, an aliphatic amino group
(typically an alkylamino group) an arylamino group and a
heterocyclic amino group. The amino group is preferably a
substituted or unsubstituted aliphatic amino group (typically an
alkylamino group) having from 1 to 30 carbon atoms, or a
substituted or unsubstituted arylamino group having from 6 to 30
carbon atoms. Examples of the amino group include an amino group, a
methylamino group, a dimethylamino groups an anilino group, an
N-methyl-anilino group, a diphenylamino group, a hydroxyethylamino
group, a carboxyethylamino group, a sulfoethylamino group, a
3,5-dicarboxyanilino group, a 4-quinolylamino group.
The acylamino group is preferably a formylamino group, a
substituted or unsubstituted alkylcarbonylamino group having from 1
to 30 carbon atoms, or a substituted or unsubstituted
arylcarbonylamino having from 6 to 30 carbon atoms. Examples of the
acylamino group include a formylamino group, an acetylamino group,
a pivaloylamino group, a lauroylamino group, a benzoylamino group,
a 3,4,5-tri-n-octyloxyphenylcarbonylamino group.
The aminocarbonylamino group is preferably a substitute or
unsubstituted aminocarbonylamino group having from 1 to 30 carbon
atoms. Examples of the aminocarbonylamino group include a
carbamoylamino group, an N,N-dimethylaminocarbonylamino group, an
N,N-diethylaminocarbonylamino group, a morpholinocarbonylamino
group. The term "amino" in this group has the same meaning as that
of the "amino" in the above-mentioned amino group.
The aliphatic oxycarbonylamino group (typically alkoxycarbonylamino
group) preferably has from 2 to 30 carbon atoms, and may have a
substituent. For example, it includes a methoxycarbonylamino group,
an ethoxycarbonylamino group, a tert-butoxycarbonylamino group, an
n-octadecyloxycarbonylamino group, an N-methyl-methoxycarbonylamino
group.
The aryloxycarbonylamino group is preferably a substituted or
unsubstituted aryloxycarbonylamino group having from 7 to 30 carbon
atoms. Examples of the aryloxycarbonylamino group include a
phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, a
m-n-octyloxyphenoxycarbonylamino group. Preferred is a
phenyloxycarbonylamino group optionally having a substituent.
The sulfamoylamino group is preferably a substituted or
unsubstituted sulfamoylamino group having from 0 to 30 carbon
atoms. Examples of the sulfamoylamino group include a
sulfamoylamino group, an N,N-dimethylaminosulfonylamino group, an
N-n-octylaminosulfonylamino group.
The aliphatic (typically alkyl) or arylsulfonylamino group is
preferably a substituted or unsubstituted aliphatic sulfonylamino
group (typically an alkylsulfonylamino group) having from 1 to 30
carbon atoms, a substituted or unsubstituted arylsulfonylamino
group having from 6 to 30 carbon atoms (preferably a
phenylsulfonylamino group optionally having a substituent). For
example, it includes a methylsulfonylamino group, a
butylsulfonylamino group, a phenylsulfonylamino group, a
2,3,5-trichlorophenylsulfonylamino group, a
p-methylphenylsulfonylamino group.
The aliphatic thio group (typically alkylthio group) is preferably
a substituted or unsubstituted alkylthio group having from 1 to 30
carbon atoms. Examples of the alkylthio group include a methylthio
group, an ethylthio group, an n-hexadecylthio group.
The sulfamoyl group is preferably a substituted or unsubstituted
sulfamoyl group having from 0 to 30 carbon atoms. Examples of the
sulfamoyl group include an N-ethylsulfamoyl group, an
N-(3-dodecyloxypropyl)sulfamoyl group, an N,N-dimethylsulfamoyl
group, an N-acetylsulfamoyl group, an N-benzoylsulfamoyl group, an
N--(N'-phenylcarbamoyl)sulfamoyl group.
The aliphatic (typically alkyl) or arylsulfinyl group is preferably
a substituted or unsubstituted aliphatic sulfinyl group (typically
an alkylsulfinyl group) having from 1 to 30 carbon atoms, a
substituted or unsubstituted arylsulfinyl group having from 6 to 30
carbon atoms (preferably a phenylsulfinyl group optionally having a
substituent). For example, it includes a methylsulfinyl group, an
ethylsulfinyl group, a phenylsulfinyl group, a
p-methylphenylsulfinyl group.
The aliphatic (typically alkyl) or arylsulfonyl group is preferably
a substituted or unsubstituted aliphatic sulfonyl group (typically
an alkylsulfonyl group) having from 1 to 30 carbon atoms, a
substituted or unsubstituted arylsulfonyl group having from 6 to 30
carbon atoms (preferably a phenylsulfonyl group optionally having a
substituent). For example, it includes a methylsulfonyl group, an
ethylsulfonyl group, a phenylsulfonyl group, a p-toluenesulfonyl
group.
The acyl group is preferably a formyl group, a substituted or
unsubstituted aliphatic carbonyl group (typically an alkylcarbonyl
group) having from 2 to 30 carbon atoms, a substituted or
unsubstituted arylcarbonyl group having from 7 to 30 carbon atoms
(preferably a phenylcarbonyl group optionally having a
substituent), a substituted or unsubstituted heterocyclic carbonyl
group having from 4 to 30 carbon atoms in which the ring bonds to
the carbonyl group via its carbon atoms. For example, it includes
an acetyl group, a pivaloyl group, a 2-chloroacetyl group, a
stearoyl group, a benzoyl group, a p-n-octyloxyphenylcarbonyl
group, a 2-pyridylcarbonyl group, a 2-furylcarbonyl group.
The aryloxycarbonyl group is preferably a substituted or
unsubstituted aryloxycarbonyl group having from 7 to 30 carbon
atoms. Examples of the aryloxycarbonyl group include a
phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, an
m-nitrophenoxycarbonyl group, a p-tert-butylphenoxycarbonyl group.
Preferred is a phenyloxycarbonyl group optionally having a
substituent.
The aliphatic oxycarbonyl group (typically alkoxycarbonyl group)
preferably has from 2 to 30 carbon atoms, and may have a
substituent. For example, it includes a methoxycarbonyl group, an
ethoxycarbonyl group, a tert-butoxycarbonyl group, an
n-octadecyloxycarbonyl group.
The carbamoyl group is preferably a substituted or unsubstituted
carbamoyl group having from 1 to 30 carbon atoms. Examples of the
carbamoyl group include a carbamoyl group, an N-methylcarbamoyl
group, an N,N-dimethylcarbamoyl group, an N,N-di-n-octylcarbamoyl
group, an N-(methylsulfonyl)carbamoyl group.
The aryl or heterocyclic azo group includes, for example, a
phenylazo group, a 4-methoxyphenylazo group, a
4-pivaloylaminophenylazo group, a 2-hydroxy-4-propanoylphenylazo
group.
The imido group includes, for example, an N-succinimide group, an
N-phthalimide group.
In addition to these, further mentioned are a hydroxyl group, a
cyano group, a nitro group, a sulfo group, a carboxyl group.
These groups may be further substituted, and the substituents for
them may be the above-mentioned substituents.
Preferably, R.sup.1 and R.sup.2 each independently represent a
substituted or unsubstituted aliphatic group having from 1 to 20
carbon atoms (typically an alkyl group, an alkenyl group, a
cycloalkyl group, more preferably an alkyl group), a substituted or
unsubstituted aryl group (preferably a phenyl group optionally
having a substituent), a substituted or unsubstituted heterocyclic
group, more preferably a substituted or unsubstituted aliphatic
group having from 1 to 10 carbon atoms (preferably an alkyl group,
an alkenyl group, a cycloalkenyl group, more preferably an alkyl
group), a substituted or unsubstituted aryl group, most preferably
an unsubstituted alkyl group having from 1 to 4 carbon atoms.
R.sup.3 is preferably a substituted or unsubstituted aliphatic
group having from 1 to 10 carbon atoms (preferably an alkyl group,
an alkenyl group, a cycloalkyl group, more preferably an alkyl
group), a substituted or unsubstituted aryl group (preferably a
phenyl group optionally having a substituent), a substituted or
unsubstituted aliphatic oxy group having from 1 to 10 carbon atoms
(preferably an alkoxy group, an alkenoxy group, a cycloalkoxy
group, more preferably an alkoxy group), or a substituted or
unsubstituted amino group (preferably an alkylamino group, an
arylamino group, an acylamino group, more preferably an acylamino
group), more preferably a substituted or unsubstituted alkyl group
having from 1 to 5 carbon atoms, a substituted or unsubstituted
alkoxy group having from 1 to 5 carbon atoms, a substituted or
unsubstituted acylamino group having from 1 to 5 carbon atoms, most
preferably an unsubstituted alkoxy group having from 1 to 3 carbon
atoms or an acylamino group having from 1 to 4 carbon atoms.
R.sup.5 is preferably a substituted or unsubstituted aliphatic
group having from 1 to 20 carbon atoms (preferably an alkyl group,
an alkenyl group, a cycloalkyl group, more preferably an alkyl
group), a substituted or unsubstituted aryl group (preferably a
phenyl group optionally having a substituent), more preferably a
substituted or unsubstituted aliphatic group having from 3 to 10
carbon atoms (preferably an alkyl group, an alkenyl group, a
cycloalkyl group, more preferably an alkyl group), most preferably
a tert-butyl group.
R.sup.6 is preferably a substituted or unsubstituted aliphatic
group having from 1 to 20 carbon atoms (preferably an alkyl group,
an alkenyl group, a cycloalkyl group, more preferably an alkyl
group), a substituted or unsubstituted aryl group (preferably a
phenyl group optionally having a substituent), more preferably a
substituted or unsubstituted aliphatic group having from 1 to 10
carbon atoms (preferably an alkyl group, an alkenyl group, a
cycloalkyl group, more preferably an alkyl group), a substituted or
unsubstituted aryl group, most preferably a substituted or
unsubstituted alkyl group having from 1 to 4 carbon atoms or a
substituted or unsubstituted aryl group.
Regarding the preferred combination of the substituents
(combination of R.sup.1, R.sup.2, R.sup.3, R.sup.5 and R.sup.6) in
the dye of formula (1) of the invention, it is desirable that at
least one of these substituent is the above-mentioned preferable
group, more preferably more various substituents are the
above-mentioned preferred groups, most preferably all the
substituents are the above-mentioned preferred groups.
One preferred combination is that R.sup.1 is a substituted or
unsubstituted alkyl group having from 1 to 4 carbon atoms, R.sup.2
is a substituted or unsubstituted alkyl group having from 1 to 4
carbon atoms, R.sup.3 is an acylamino group, R.sup.5 is a
substituted or unsubstituted alkyl group having from 1 to 4 carbon
atoms, R.sup.6 is a substituted or unsubstituted alkyl group having
from 1 to 4 carbon atoms, or a substituted or unsubstituted aryl
group, and n=1 (in which the substituting position of R.sup.3 is
preferably an ortho position relative to the azo group).
A more preferred combination is that R.sup.1 is a substituted or
unsubstituted alkyl group having from 1 to 4 carbon atoms, R.sup.2
is a substituted or unsubstituted alkyl group having from 1 to 4
carbon atoms, R.sup.3 is an acylamino group, R.sup.5 is a
tert-butyl group, R.sup.6 is a substituted or unsubstituted alkyl
group having from 1 to 4 carbon atoms, or a substituted or
unsubstituted aryl group, and n=1 (in which the substituting
position of R.sup.3 is preferably an ortho position relative to the
azo group).
A most preferred combination is that R.sup.1 is a substituted or
unsubstituted alkyl group having from 1 to 4 carbon atoms, R.sup.2
is a substituted or unsubstituted alkyl group having from 1 to 4
carbon atoms, R.sup.3 is an acylamino group, R.sup.5 is a
tert-butyl group, R.sup.6 is a substituted or unsubstituted alkyl
group having from 1 to 2 carbon atoms, or a substituted or
unsubstituted phenyl group, and n=1 (in which the substituting
position of R.sup.3 is preferably an ortho position relative to the
azo group); or the azo dye of formula (2).
The molecular weight of the azo dye of formula (1) is preferably at
most 550, more preferably at most 500 from the viewpoint of the
thermal diffusibility thereof.
[Azo Dye of Formula (2)]
The azo dye of formula (2) is described in detail hereinunder.
The azo dye of formula (2) is characterized in that, in addition to
the characteristic structure of the azo dye of formula (1), the
aniline group has a substituted amino group as the substituent; and
the dye having those characteristics are quite unknown up to the
present. The azo dye of formula (2) having the characteristics has
a sharper absorption and is faster than the azo dye of formula (1).
Accordingly, the dye of formula (2), falling within the scope of
the dye of formula (1), is especially more favorable for use in the
above-mentioned thermal transfer recording ink sheet, and, in
addition, it is also favorable for other applications (e.g.,
ink).
In formula (2), R.sup.1, R.sup.2, R.sup.3, R.sup.5 and R.sup.6 have
the same meanings as those of R.sup.1, R.sup.2, R.sup.3, R.sup.5
and R.sup.6 in formula (1). Preferred examples of R.sup.1, R.sup.2,
R.sup.5 and R.sup.6 are also the same as those of the latter. In
formula (2), m indicates an integer of from 0 to 3, and m is
preferably 0.
In formula (2), R.sup.4 represents a monovalent substituent. The
monovalent substituent is not specifically defined. Its typical
examples include an aliphatic group (e.g., an alkyl group, an
alkenyl group, an alkynyl group), an aryl group, a heterocyclic
group, an acyl group, an aryloxycarbonyl group, an aliphatic
oxycarbonyl group (e.g., an alkoxycarbonyl group), a carbamoyl
group. These groups may be further substituted.
Preferably, it is a substituted or unsubstituted acyl group having
from 1 to 8 carbon atoms, more preferably an unsubstituted acyl
group having from 1 to 6 carbon atoms, most preferably an
unsubstituted acyl group having from 1 to 4 carbon atoms.
Regarding the preferred combination of the substituents
(combination of R.sup.1 to R.sup.6) in the dye of formula (2) of
the invention, it is desirable that at least one of these
substituent is the above-mentioned preferable group, more
preferably more various substituents are the above-mentioned
preferred groups, most preferably all the substituents are the
above-mentioned preferred groups.
One preferred combination is that R.sup.1 is a substituted or
unsubstituted alkyl group having from 1 to 4 carbon atoms, R.sup.2
is a substituted or unsubstituted alkyl group having from 1 to 4
carbon atoms, R.sup.4 is an acyl group, R.sup.5 is a substituted or
unsubstituted alkyl group having from 1 to 4 carbon atoms, R.sup.6
is a substituted or unsubstituted alkyl group having from 1 to 4
carbon atoms, or a substituted or unsubstituted aryl group, and
m=0.
A more preferred combination is that R.sup.1 is a substituted or
unsubstituted alkyl group having from 1 to 4 carbon atoms, R.sup.2
is a substituted or unsubstituted alkyl group having from 1 to 4
carbon atoms, R.sup.4 is an acyl group, R.sup.5 is a tert-butyl
group, R.sup.6 is a substituted or unsubstituted alkyl group having
from 1 to 4 carbon atoms, or a substituted or unsubstituted aryl
group, and m=0.
A most preferred combination is that R.sup.1 is a substituted or
unsubstituted alkyl group having from 1 to 4 carbon atoms, R.sup.2
is a substituted or unsubstituted alkyl group having from 1 to 4
carbon atoms, R.sup.4 is an acyl group, R.sup.5 is a tert-butyl
group, R.sup.6 is a substituted or unsubstituted alkyl group having
from 1 to 2 carbon atoms, or a substituted or unsubstituted phenyl
group, and m=0.
Specific examples of the azo dye of formula (1) of the invention
are shown below; however, the azo dye of formula (1) for use in the
invention should not be limitatively interpreted by the following
examples. In the following examples, Ph means a phenyl group
(--C.sub.6H.sub.5).
##STR00004## ##STR00005##
The above compounds (1) to (8) are examples of the azo dye of
formula (2); and the above compounds (9) and (10) are similar to
the synthetic intermediates described in U.S. Pat. No.
3,515,715.
These azo dyes may be produced through general diazo coupling
followed by N-sulfonylation with sulfonyl chloride.
Concretely, the amino group of an aminopyrazole derivative of the
following formula (3) is converted into a diazonium salt as in the
following formula (4), using a diazonating agent, then the
diazonium salt is coupled with an aniline derivative of the
following formula (5), thereby obtaining a compound of the
following formula (6). Afterwards, the compound of formula (6) is
N-sulfonylated with a compound of the following formula (7) under a
basic condition, thereby readily producing the intended dye
compound. The process is concretely demonstrated in Examples given
hereinunder.
##STR00006## (In the formulae, R.sup.1 to R.sup.6 have the same
meanings as those of R.sup.1 to R.sup.6 in the above-mentioned
formula (1). X.sup.1 represents a counter anion of the diazonium,
salt of formula (4); and X.sup.2 represents a halogen atom.)
Many of the compounds of formulae (5) and (7) are readily available
as commercial products (e.g., Wako Pure Chemicals' catalogue Nos.
329-30252, 135-01586). The compound of formula (3) may be produced
according to the method described in J. Am. Chem. Soc., 124, 41, p.
12118, 2002.
The azo dye of the invention is preferably used as a magenta color
of three primary colors.
The maximum absorption wavelength of the azo dye of the invention
preferably falls within a range of from 480 to 580 nm, more
preferably from 510 to 550 nm.
[Coloring Composition]
The coloring composition of the invention is characterized by
containing the dye of formula (1) of the invention. The coloring
composition in this description is directed to thermal transfer
recording ink sheets, inkjet inks, color toners, color filters,
writing pens, color plastics, and other ink liquids.
The coloring composition of the invention is especially effectively
used for thermal transfer recording ink sheets, inkjet inks, color
toners, and color filters.
[Thermal Transfer Recording Ink Sheet]
The thermal transfer recording ink sheet of the invention is
characterized by containing the dye of formula (1). The thermal
transfer recording ink sheet generally has a structure with a
dye-donating layer formed on a support, in which the dye-donating
layer contains a dye of formula (1). The thermal transfer recording
ink sheet of the invention may be produced as follows: A dye of
formula (1) is dissolved in a solvent along with a binder therein
or dispersed as particles in a solvent, thereby preparing an ink
liquid, then the ink liquid is applied onto a support and suitably
dried to form a dye-donating layer thereon.
As the support of the thermal transfer recording ink sheet of the
invention, any ordinary one heretofore used as a support for ink
sheets may be suitably selected and used. For example, the material
described in JP-A 7-137466, paragraph [0050] may be favorably used.
The thickness of the support is preferably from 2 to 30 .mu.m.
Not specifically defined, the binder resin usable in the
dye-donating layer of the thermal transfer recording ink sheet of
the invention may be any one having high heat resistance and not
interfering with the transference of the dye into an
image-receiving material when heated. For example, its preferred
examples are described in JP-A 7-137466, paragraph [0049]. The
solvent for dye-donating layer formation may also be any
conventional known one; and those described in JP-A 7-137466,
Examples are favorably used also herein.
The content of the dye of formula (1) in the dye-donating layer is
preferably from 0.03 to 1.0 g/m.sup.2 more preferably from 0.1 to
0.6 g/m.sup.2 The thickness of the dye-donating layer is preferably
from 0.2 to 5 an, more preferably from 0.4 to 2 .mu.m.
The thermal transfer recording ink sheet of the invention may have
any other layer than the dye-donating layer within a range not too
much detracting from the effect of the invention. For example, an
interlayer may be provided between the support and the dye-donating
layer; or a back layer may be provided on the surface of the
support opposite to the side of the dye-donating layer (this is
hereinafter referred to as "back surface"). The interlayer
includes, for example, an undercoating layer, and a
diffusion-preventing layer for preventing the dye from diffusing
toward the support (hydrophilic barrier layer). The back layer is,
for example, a heat-resistant slip layer, which is for preventing a
thermal head from sticking to the ink sheet.
In case where the invention is applied to thermal transfer
recording material that enables full-color image recording, it is
desirable that a cyan ink sheet containing a thermal diffusible
cyan dye capable of forming cyan images, a magenta ink sheet
containing a thermal diffusible magenta dye capable of forming
magenta images, and a yellow ink sheet containing a thermal
diffusible yellow dye capable of forming yellow images are formed
successively on a support. If desired, an ink sheet containing a
black image-forming substance may be further formed.
As the thermal diffusible cyan dye-containing cyan ink sheet for
forming cyan images, for example, preferably used are those
described in JP-A 3-103477, 3-150194. As the thermal diffusible
yellow dye-containing yellow ink sheet for forming yellow images,
for example, preferably used are those described in JP-A
1-225592.
[Thermal Transfer Recording]
In thermal transfer recording by the use of the thermal transfer
recording ink sheet of the invention, a heating unit such as a
thermal head and an image-receiving material are used as combined.
Specifically, heat energy is applied to the ink sheet from a
thermal head according to an image recording signal, and the dye in
the part having received the heat energy is transferred to and
fixed in an image-receiving material to attain image recording. The
image-receiving material generally has a constitution with a
polymer-containing ink-receiving layer formed on a support. As the
constitution and the constitutive components of the image-receiving
material, for example, preferably used are those described in JP-A
7-137466, paragraphs [0056] to [0074].
[Color Toner]
The color toner of the invention is characterized by containing the
dye of formula (1). As the binder resin for color toner into which
the dye (preferably azo dye) of formula (1) of the invention is
introduced, usable is any and every binder for general use in
toner. For example, it includes styrene resin, acrylic resin,
styrene/acrylic resin, polyester resin. For the purpose of
improving the flowability of the toner and for static control
thereof, an inorganic fine powder or organic fine particles may be
added to the toner as external additives. Preferably used are
silica particles and titania particles of which the surfaces are
processed with an alkyl group-containing coupling agent or the
like. Preferably, the particles have a number-average primary
particle size of from 10 to 500 nm; and also preferably, the
particles are added to the toner in an amount of from 0.1 to 20% by
mass.
As the lubricant, any and every lubricant heretofore used in toner
may be used herein. Concretely, it includes olefins such as
low-molecular-weight polypropylene, low-molecular-weight
polyethylene, ethylene-propylene copolymer; and microcrystalline
wax, carnauba wax, Sasol wax, paraffin wax. Preferably, the
lubricant is added to the toner in an amount of from 1 to 5% by
mass.
If desired, a charge-controlling agent may be added to the toner,
and it is preferably colorless from the viewpoint of the
colorability of the toner. For example, herein usable are those
having a quaternary ammonium salt structure or a calixarene
structure.
The carrier may be any of a non-coated carrier formed of magnetic
material particles alone of iron, ferrite or the like; or a
resin-coated carrier prepared by coating the surfaces of magnetic
material particles with resin or the like. Regarding the mean
particle size thereof, the carrier preferably has a volume-average
particle size of from 30 to 150 .mu.m.
The image-forming method to which the toner of the invention is
applicable is not specifically defined. For example, the toner is
applicable to an image-forming method that comprises repeatedly
forming a color image on a photoreceptor followed by transferring
it; and a color image-forming method that comprises transferring an
image formed on a photoreceptor successively onto an intermediate
transfer medium thereby forming a color image on the intermediate
transfer medium, followed by transferring the image onto an
image-forming member such as paper.
[Inkjet Ink]
The inkjet ink of the invention is characterized by containing the
dye of formula (1). The ink of the invention may be produced by
dissolving and/or dispersing the dye of formula (1) in an
oleophilic medium or an aqueous medium, and preferably an aqueous
medium is used. The ink of the invention contains the dye having
excellent spectral characteristics and fastness as so mentioned in
the above, and is therefore favorably used as an inkjet recording
ink. If desired, other additives may be added to the ink within a
range not detracting from the effect of the invention. The
additives may be known additives, including, for example, a drying
inhibitor (wetting agent), an antifading agent, a emulsion
stabilizer, a penetration promoter, a UV absorbent, a preservative,
an antifungal agent, a pH controlling agent, a surface tension
controlling agent, a defoaming agent, a viscosity controlling
agent, a dispersant, a dispersion stabilizer, a rust inhibitor, a
chelating agent. In general, these various additives are added to
the dye dispersion after its preparation, but as the case may be,
they may be added to an oily phase or an aqueous phase in preparing
the dye dispersion.
The drying inhibitor is favorably used for the purpose of
preventing the inkjet ink from drying at the ink-jetting orifice of
the nozzle used in an inkjet recording system.
The drying inhibitor is preferably a water-soluble organic solvent
having a vapor pressure lower than water. Its concrete examples
include polyalcohols such as typically ethylene glycol, propylene
glycol, diethylene glycol, polyethylene glycol, thiodiglycol,
dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol,
acetylene glycol derivative, glycerin, trimethylolpropane;
polyalcohol lower alkyl ethers such as ethylene glycol monomethyl
(or ethyl)ether, diethylene glycol monomethyl (or ethyl)ether,
triethylene glycol monoethyl (or butyl)ether; heterocyclic
compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone,
1,3-dimethyl-2-imidazolidinone, N-ethylmorpholine;
sulfur-containing compounds such as sulfolane, dimethyl sulfoxide,
3-sulfolene; polyfunctional compounds such as diacetone alcohol,
diethanolamine; and urea derivatives. Of those, more preferred are
polyalcohols such as glycerin, diethylene glycol. One or more of
the above drying inhibitors may be used either singly or as
combined. The drying inhibitor may be in the ink preferably in an
amount of from 10 to 50% by mass.
The penetration promoter is favorably used for the purpose of more
rapidly penetrating the inkjet ink into paper. As the penetration
promoter, usable are alcohols such as ethanol, isopropanol,
butanol, di(tri)ethylene glycol monobutyl ether, 1,2-hexanediol;
sodium laurylsulfate, sodium oleate, nonionic surfactant. When the
agent is in the ink in an amount of from 5 to 30% by mass, then it
is generally sufficiently effective. Preferably, the agent is used
in an amount not causing print blur and print through.
The UV absorbent is used for the purpose of improving the image
storability. The UV absorbent includes benzotriazole compounds as
in JP-A 58-185677, 61-190537, 2-782, 5-197075, 9-34057;
benzophenone compounds as in JP-A 46-2784, 5-194483, U.S. Pat. No.
3,214,463; cinnamic acid compounds as in UP-B 48-30492, 56-21141,
JP-A 10-88106; triazine compounds as in JP-A 4-298503, 8-53427,
8-239368, 10-182621, JP-T 8-501291; and also the compounds
described in Research Disclosure No. 24239, and compounds capable
of absorbing UV rays to emit fluorescent light, or that is,
fluorescent brighteners such as typically stilbene compounds and
benzoxazole compounds.
The antifading agent is used for the purpose of improving the image
storability. As the antifading agent, usable are various organic or
metal complex-type antifading agents. The organic antifading agent
includes hydroquinones, alkoxyphenols, dialkoxyphenols, phenols,
anilines, amines, indanes, chromans, alkoxyanilines, and
heterocyclic compounds; and the metal complex includes nickel
complexes and zinc complexes. More concretely, herein usable are
the compounds described in the patent references cited in Research
Disclosure No. 17643, Items VII-I to J, ibid., No. 15162, ibid.,
No. 18716, page 650, left column, ibid., No. 36544, page 527,
ibid., No. 307105, page 872, ibid., No. 15162; and the compounds
falling within the scope of the typical compounds of the formula
and the examples of the compounds described in JP-A 62-215272, pp.
127 to 137.
The rust inhibitor includes sodium dehydroacetate, sodium benzoate,
sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate,
1,2-benzisothiazolin-3-one and its salts. Preferably, this is in
the ink in an amount of from 0.02 to 1.00% by mass.
As the pH controlling agent, usable are neutralizing agents
(organic base, inorganic alkali). For the purpose of improving the
storage stability of the inkjet ink, the pH controlling agent is
preferably added to the inkjet ink so that the ink could have a pH
of from 6 to 10, more preferably from 7 to 10.
The surface tension controlling agent may be a nonionic, cationic
or anionic surfactant. Preferably, the surface tension of the
inkjet ink containing the coloring composition of the invention is
from 20 to 60 mN/m, more preferably from 25 to 45 mN/m. The
viscosity of the inkjet ink of the invention is preferably at most
30 mPas, more preferably so controlled as to be at most 20
mPas.
Preferred examples of the surfactant include anionic surfactants
such as fatty acid salts, alkylsulfate ester salts,
alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic salts,
dialkylsulfosuccinic acid salts, alkylphosphate ester salts,
naphthalenesulfonic acid/formalin condensates, polyoxyethylene
alkylsulfate ester salts; and nonionic surfactants such as
polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers,
polyoxyethylene fatty acid esters, sorbitan fatty acid esters,
polyoxyethylene sorbitan fatty acid esters, polyoxyethylene
alkylamines, glycerin fatty acid esters, oxyethylene-oxypropylene
block copolymers. Also preferred are SURFYNOLS (trade name by Air
Products & Chemicals) that are acetylene-type polyoxyethylene
oxide surfactants.
Also preferred are amine oxide-type ampholytic surfactants such as
N,N-dimethyl-N-alkylamine oxide. Further usable herein are the
surfactants described in JP-A 59-157636, pp. 37-38, and Research
Disclosure No. 308119 (1989).
As the defoaming agent, optionally used herein are fluorine
compounds, silicone compounds, and chelating agents such as
EDTA.
In case where the dye of formula (1) is dispersed in an aqueous
medium, it is desirable that coloring particles containing the
compound and an oil-soluble polymer are dispersed in an aqueous
medium as in JP-A 11-286637, 2001-240763, 2001-262039, 2001-247788,
or the dye of formula (1) dissolved in a high-boiling-point organic
solvent is dispersed in an aqueous medium as in JP-A 2001-262018,
2001-240763, 2001-335734, 2002-80772. Regarding the concrete method
of dispersing the dye of formula (1) in an aqueous medium, as well
as the oil-soluble polymer, the high-boiling-point organic solvent
and the additives to be used, and their amounts those described in
the above-mentioned patent references are employable herein. As the
case may be, the bisazo compound may be dispersed as fine particles
directly as it is solid. In dispersing them, a dispersant and a
surfactant may be used.
As the dispersing device, usable are simple stirrers, and also
impellers, in-line stirrer mills (e.g., colloid mill, ball mill,
sand mill, attritor, roll mill, agitator mill), ultrasonic
stirrers, high-pressure emulsification dispersers (high-pressure
homogenizers; as commercial devices, available are Gaulin
homogenizer, Microfluidizer, DeBEE 2000 (by BEE International)).
Regarding the method of preparing the above-mentioned inkjet
recording ink, its details are described also in JP-A 5-148436,
5-295312, 7-97541, 7-92515, 7-118584, 11-286637, 2001-271003, in
addition to the above-mentioned patent references; and these
descriptions are applicable to the preparation of the inkjet
recording ink of the invention.
As the aqueous medium, usable is a mixture comprising water as the
main ingredient and optionally containing a water-miscible organic
solvent added thereto. Examples of the water-miscible organic
solvent include alcohols (e.g., methanol, ethanol, n-propanol,
isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol,
hexanol, cyclohexanol, benzyl alcohol), polyalcohols (e.g.,
ethylene glycol, diethylene glycol, triethylene glycol,
polyethylene glycol, propylene glycol, dipropylene glycol,
polypropylene glycol, butylene glycol, hexanediol, pentanediol,
glycerin, hexanetriol, thiodiglycol), glycol derivatives (e.g.,
ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
ethylene glycol monobutyl ether, diethylene glycol monomethyl
ether, diethylene glycol monobutyl ether, propylene glycol
monomethyl ether, propylene glycol monobutyl ether, dipropylene
glycol monomethyl ether, triethylene glycol monomethyl ether,
ethylene glycol diacetate, ethylene glycol monomethyl ether
acetate, triethylene glycol monomethyl ether, triethylene glycol
monoethyl ether, ethylene glycol monophenyl ether), amines (e.g.,
ethanolamine, diethanolamine, triethanolamine,
N-methyldiethanolamine, N-ethyldiethanolamine, morpholine,
N-ethylmorpholine, ethylenediamine, diethylenetriamine,
triethylenetetramine, polyethyleneimine,
tetramethylpropylenediamine), and other polar solvents (e.g.,
formamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl
sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone,
N-vinyl-2-pyrrolidone, 2-oxazolidone,
1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). Two or more
of the above-mentioned water-miscible organic solvents may be
combined for use herein.
[Color Filter]
The color filter of the invention is characterized by containing
the dye of formula (1). For producing the color filter, employable
is a method of first forming a pattern with a photoresist and then
dying it; or a method of forming a pattern with a photoresist to
which a colorant is added, as in JP-A 4-163552, 4-126703, 4-175753.
As the method of introducing the dye of formula (1) into the color
filter of the invention, any of the above methods is employable,
but preferred is the method described in JP-A 4-175753, 6-35182.
The method comprises applying a positive photoresist composition
containing a thermosetting resin, a quinonediazide compound, a
crosslinking agent, a colorant and a solvent, onto a support, then
exposing it through a mask, developing the exposed area to form a
positive resist pattern, then exposing the entire surface of the
positive resist pattern to light, and thereafter curing the
thus-exposed positive resist pattern to produce a color filter.
Also employable is a method of forming a black matrix in an
ordinary manner thereby obtaining an RGB primary color filter or an
Y.M.C complementary color filter.
For the thermosetting resin, the quinonediazide compound, the
crosslinking agent and the solvent to be used in the above and
their amount, preferred are those described in the above-mentioned
patent references.
EXAMPLES
The characteristics of the invention are described more concretely
with reference to Production Examples and Examples given below.
In the following Examples, the material used, its amount and the
ratio, the details of the treatment and the treatment process may
be suitably modified or changed not overstepping the scope of the
invention. Accordingly, the invention should not be limitatively
interpreted by the Examples mentioned below.
Example 1
Production and Evaluation of Dye
<Production of Compound (1)>
##STR00007## (Production of Intermediate (A))
5-Amino-3-tert-butyl-1H-pyrazole-4-carbonitrile (19.9 g, 0.121 mol)
was dissolved in acetic acid (25 mL), propionic acid (35 mL) and
concentrated hydrochloric acid (36 mL), and cooled to an inner
temperature of 0.degree. C. With keeping the inner temperature at
5.degree. C. or lower, a solution prepared by dissolving sodium
nitrite (8.8 g) in water (18 mL) was gradually dropwise added to
it; and after the addition, this was stirred at an inner
temperature of from 0 to 5.degree. C. for 30 minutes (diazo
solution). Apart from it, 3'-(diethylamino)acetanilide (25 g) was
dissolved in acetonitrile (800 mL), and cooled to an inner
temperature of 10.degree. C. or lower; and the diazo solution
prepared in the above was gradually added to it. This was stirred
at an inner temperature of not higher than 10.degree. C. for 1 hour
and then at room temperature for 1 hour, and the precipitated
crystal was taken out by filtration and washed with acetonitrile to
obtain a yellow crystal of the intermediate (A) (yield: 38.4 g,
83.2%)
(Production of Compound (1))
The intermediate (A) (5.7 g, 0.015 mol), N,N-dimethylacetamide (75
mL), triethylamine (8 mL) were mixed, then cooled to an inner
temperature of 5.degree. C. or lower, and methanesulfonyl chloride
(15 mL) was dropwise added, then stirred at 35 to 45.degree. C. for
7 hour. The reaction liquid was poured into water, the precipitated
crystal was taken out by filtration, and recrystallized with
acetonitrile to obtain a powder of the compound (1) (yield: 2.6 g,
43%; melting point: 205.degree. C.).
.lamda.max of the compound (1) (in ethyl acetate solution) was 541
nm.
<Production of Compounds (2), (5) and (10)>
Compounds (2), (5) and (10) were produced according to the method
of the above Production Example. Other compounds than the compounds
(1), (2), (5) and (10) may also be produced according to the method
of the above-mentioned Production Example from the chemical
viewpoint.
<Evaluation>
The thus-obtained compounds (1), (2), (5) and (10) were analyzed
absorption spectrometry in an ethyl acetate solution
(concentration: 1.times.10.sup.-6 mol/L, optical path length: 10
mm). The data of the maximum absorption wavelength of the compounds
are shown in the following Table 1.
TABLE-US-00001 TABLE 1 Dye Maximum Absorption Wavelength (nm) (1)
541 (2) 548 (5) 539 (10) 506
Example 2
Construction and Evaluation of Thermal Transfer Recording Ink
Sheet
<Construction of Thermal Transfer Recording Ink Sheet>
A polyester film (Lumirror, trade name by Toray) having a thickness
of 6.0 .mu.m and processed for heat-resistant lubrication with a
thermosetting acrylic resin (thickness 1 .mu.m) on its back was
used as a support. Using a wire bar coater, a dye-donating
layer-forming coating composition mentioned below was applied onto
the surface of the film to form thereon a layer having a dry
thickness of 1 .mu.m, thereby constructing an ink sheet 1.
TABLE-US-00002 (Dye-Donating Layer-Forming Coating Composition)
Compound (1) 5.5 mas. pts. Polyvinylbutyral Resin (Eslec BX-1,
trade name 4.5 mas. pts. by Sekisui Chemical Industry) Methyl ethyl
ketone/toluene (1/1) 90 mas. pts.
Next, ink sheets 2 to 4 of the invention and comparative ink sheets
5 to 7 were constructed in the same manner as that for the ink
sheet 1, for which, however, the compound (1) was changed to the
dye shown in Table 2 below. The dye solubility was ranked in three,
A (easily soluble), B (soluble) r C (difficult to dissolve, but
soluble). The results are shown in Table 2.
<Construction of Image-Receiving Material>
Synthetic paper (Yupo FPG200, trade name by Yupo Corporation,
thickness: 200 .mu.m) was used as a support. A white
interlayer-forming coating composition and a receiving
layer-forming coating composition mentioned below were applied in
that order onto one surface of the support, using a bar coater.
Their amount was so controlled that the white interlayer could have
a dry thickness of 1.0 g/m.sup.2 and the receiving layer could have
a dry thickness of 4.0 g/m.sup.2. The layers were dried at
110.degree. C. for 30 seconds each.
TABLE-US-00003 (White Interlayer-Forming Coating Composition)
Polyester resin (Vylon 200, trade name by 10 mas. pts. TOYOBO)
Fluorescent brightener (Uvitex OB, trade name 1 mas. pt. by
Ciba-Geigy) Titanium oxide 30 mas. pts. Methyl ethyl ketone/toluene
(1/1) 90 mas. pts. (Receiving Layer-Forming Coating Composition)
Vinyl chloride-vinyl acetate resin (Solbine A, 100 mas. pts. trade
name by Nisshin Chemical Industry) Amino-modified silicone
(X22-3050C, trade name 5 mas. pts. by Shin-etsu Chemical Industry)
Eposy-modified silicone (X22-300E, trade name 5 mas. pts. by
Shin-etsu Chemical Industry) Methyl ethyl ketone/toluene (=1/1) 400
mas. pts. Benzotriazole-type UV absorbent (Tinuvin 900, 5 mas. pts.
trade name by Ciba Speciality Chemicals)
<Image Recording and Evaluation>
The ink sheet 1 and the image-receiving material constructed as
above were combined in such a manner that the dye-donating layer
could face the image-receiving layer, and this was printed using a
thermal head applied to the back of the dye-donating material. The
output power of the thermal head was 0.25 W/dot, pulse width was
from 0.15 to 15 msec, the dot density was 6 dots/mm. In that
manner, the magenta dye was imagewise fixed on the image-receiving
layer of the image-receiving material, and as a result, a sharp
image print with no transfer unevenness was obtained. The ink
sheets 2 to 8 were used in place of the ink sheet 1, tested for
image recording.
The solid density (100% dot density) of each image was measured as
the status A reflection density thereof, and the samples were
evaluated for their transferability in 3 ranks, as follows: Those
having a reflection density of at least 1.8 are excellent, A; those
having from 1.6 to less than 1.8 are good, B; those having from 1.0
to less than 1.6 are average, C. The results are shown in Table 2
below.
Next, the recorded samples were exposed to an Xe light (17000 lux)
for 7 days, and tested for the light stability (light fastness) of
the recorded images. After the exposure, the status A reflection
density of the part of each sample having an original status A
reflection density of 1.0 before the exposure was measured, and the
retention (by percentage) to the reflection density of 1.0 after
exposure to that before exposure indicates the image stability.
With the retention percentage, the samples were ranked in three, A
(from 80% to less than 100%), B (from 60% to less than 80%), C
(less than 60%). The results are shown in Table 2 below.
TABLE-US-00004 TABLE 2 Ink Light Sheet Dye Solubility
Transferability Fastness Remarks 1 (1) A A A the Invention 2 (2) A
A A the Invention 3 (5) A A A the Invention 4 (10) A A A the
Invention 5 Comparative B A C Comparative Dye 1 Example 6
Comparative B A B Comparative Dye 2 Example 7 Comparative B B C
Comparative Dye 3 Example Comparative Dye 1 (similar to Dye 9 in
U.S. Pat. No. 4,764,178): ##STR00008## Comparative Dye 2 (similar
to Dye 9 in U.S. Pat. No. 4,764,178): ##STR00009## Comparative Dye
3 (Compound 1 in JP-A 4-265797): ##STR00010##
As a result of the above image recording test, it is known that the
images transferred onto the image-receiving layer from the ink
sheets having the azo dye of formula (1) of the invention has a
sharp color, and as compared with those from the comparative dyes,
the images have more improved stability to light and have excellent
image storability.
Unexpectedly, in addition, it is known that, as compared with the
comparative dyes, the azo dyes of formula (1) of the invention have
more excellent solubility, and therefore can greatly reduce the
load in dissolution in ink sheet construction, and that the
transfer sensitivity of the dyes is excellent and therefore the
dyes can solve both the problems of the solubility and the
transferability that have heretofore been said difficult to
solve.
Example 3
Formation and Evaluation of Color Toner
<Formation of Color Toner>
3 parts by mass of an azo dye of the invention (compound (1)) and
100 parts by mass of a toner resin [styrene-acrylate copolymer,
Himer TB-1000F (trade name by Sanyo Chemical)] were mixed and
ground in a ball mill, then melted and kneaded under heat at
150.degree. C., and after cooled, this was roughly ground with a
hammer mill, and then finely ground with an air jet-type grinder.
Further classified, particles of from 1 to 20 .mu.m in size were
selected to be a toner.
<Evaluation>
10 parts by mass of the toner was uniformly mixed with 900 parts by
mass of a carrier iron powder (EFV250/400, trade name by Nippon
Iron Powder) to prepare a developer. The developer was tested for
copying with a dry-type plain paper electrophotographic copier
(NP-5000, trade name by Canon). As a result, the developer had
excellent spectral characteristics and had excellent properties as
toner.
Example 4
Formation and Evaluation of Inkjet Ink
<Formation of Inkjet Ink>
An azo dye of the invention (compound (1)) (5.63 g) and sodium
dioctylsulfosuccinate (7.04 g) were dissolved in a
high-boiling-point organic solvent mentioned below (S-2) (4.22 g),
a high-boiling-point organic solvent mentioned below (S-11) (5.63
g) and ethyl acetate (50 ml) at 70.degree. C. With stirring with a
magnetic stirrer, deionized water (500 ml) was added to the
solution to produce an oil-in-water crude particle dispersion.
Next, the crude particle dispersion was led to pass through a
microfluidizer (by MICROFLUIDEX INC) five times under a pressure of
60 MPa to be fine particles, and the thus-prepared emulsion was
evaporated for solvent removal with a rotary evaporator until it
gave no ethyl acetate odor.
Diethylene glycol (140 g), glycerin (50 g), SURFYNOL 465 (trade
name by Air Products & Chemicals) (7 g) and deionized water
(900 ml) were added to the fine emulsion of the hydrophobic dye
thus obtained as above, thereby producing an inkjet ink.
##STR00011## <Evaluation>
The thus-obtained ink was filled in a cartridge of an inkjet
printer (PM-G800, trade name by Seiko Epson), and tested in the
printer for image recording on inkjet paper, Kassai Photofinish Pro
(trade name by FUJIFILM). The reflection spectrum of the
thus-formed image is shown in FIG. 1. As is obvious from the data
in FIG. 1, it is known that the obtained image has excellent
spectral characteristics and the ink has excellent properties as
inkjet ink.
Example 5
Construction and Evaluation of Color Filter
<Construction of Color Filter>
(Preparation of Positive Resist Composition)
3.4 parts by mass of cresol/novolak resin obtained from a mixture
of m-cresol/p-cresol/formaldehyde (reaction molar ratio=5/5/7.5)
(polystyrene-based mass-average molecular weight, 4300), 1.6 parts
by mass of o-naphthoquinonediazido-5-sulfonate ester produced by
the use of a phenol compound having a formula mentioned below (in
which 2 hydroxyl groups were esterified on average), 0.8 parts by
mass of hexamethoxymethylolated melamine, 20 parts by mass of ethyl
lactate, and 1 part by mass of the compound (1) were mixed to
produce a positive resist composition.
Phenolic Compound:
##STR00012## (Construction of Color Filter)
The obtained positive resist composition was applied onto a silicon
wafer in a mode of spin coating, and the solvent was evaporated
away. Next, the silicon wafer was exposed to light through a mask
to decompose the quinonediazide compound. Next, this was heated at
100.degree. C. and then the exposed area was removed by alkali
development to obtain a positive color pattern having a resolution
of 0.8 .mu.m. This was exposed on the entire surface, and then
heated at 150.degree. C. for 15 minutes to produce a
magenta-complementary color filter. For the exposure, used was an
i-ray exposure stepper HITACHI LD-5010-i (trade name by Hitachi, NA
0.40). As the developer, used was SOPD or SOPD-B (trade name by
Sumitomo Chemical Industry).
<Evaluation>
The transmission spectrum of the obtained color filter is shown in
FIG. 2. As is obvious from the data in FIG. 2, the obtained color
filter has excellent spectral characteristics and light
transmittance, and has excellent properties as color filter.
According to the invention, there are provided a novel azo dye
having excellent spectral characteristics with sharp absorption,
high fastness and excellent solubility, and a coloring composition
containing the azo dye. According to the invention, there are also
provided a thermal transfer recording ink sheet and a thermal
transfer recording method capable of satisfying all the
requirements of excellent color reproducibility, image storability
and transfer sensitivity in print samples. The ink sheet is
excellent in that the working load and the environmental load in
producing it are greatly reduced. Further, the invention provides a
color toner, an inkjet ink and a color filter comprising the azo
dye. Accordingly, the invention is expected to be effectively used
in high-quality full color recording, and its industrial
applicability is great.
The present disclosure relates to the subject matter contained in
Japanese Patent Application No. 092233/2007 filed on Mar. 30, 2007,
which is expressly incorporated herein by reference in its
entirety. All the publications referred to in the present
specification are also expressly incorporated herein by reference
in their entirety.
The foregoing description of preferred embodiments of the invention
has been presented for purposes of illustration and description,
and is not intended to be exhaustive or to limit the invention to
the precise form disclosed. The description was selected to best
explain the principles of the invention and their practical
application to enable others skilled in the art to best utilize the
invention in various embodiments and various modifications as are
suited to the particular use contemplated. It is intended that the
scope of the invention not be limited by the specification, but be
defined claims set forth below.
* * * * *